University of Leicester Materials Centre Plastics from potatoes and rubber from rice
Polymer vs Plastics Polymer is a macromolecules containing monomers Typical polymer chain is 0.2 to 2 µm in length Held together by knots which untangle as we heat them up A plastic is a material made from a polymer with a range of additives
Polymer Monomer Scale / 10 6 t p.a. HDPE Rigid plastics 80 LDPE Flexible plastics e.g. bags PP Bottle tops 50 PVC Window frames 18 55 Common polymers Monomers need to be simple to make 7 of the world s top 20 chemicals are monomers PS Rigid plastics 15 PET HOC 2 H 4 OH Plastic bottles 28 Nylon HOOC(CH 2 ) 4 COOH Strong fibres, ropes 36 H 2 N(CH 2 ) 6 NH 2 Polybutadiene Rubber 17
Plastics Annual requirements of thermoplastics has increased from around 5 million tonnes in the 1950s to nearly 335 million tonnes today That would cover Hyde Park to the height of the Shard! One tonne of plastics is equivalent to 20,000 two litre drinks bottles or 120,000 carrier bags. Plastics makes up around 7% of the average household dustbin About 7% of oil is used to make plastic
Plastic uses Packaging uses increasing Media focus on plastic packaging Plastics are excellent for building and construction They are useful for food preservation They need to be disposed of properly
Plastic Disposal Since 1950s 8.3 bn tonnes of plastic have been produced Only 7% of plastic has ever been recycled
Plastic in the Environment
Waste Management Estimated that 20 countries are responsible for 83% of the plastic in the world s oceans. Of 275 million metric tons of plastic waste each year 4.8 12.7 million of mismanaged plastic waste end up in the oceans (2-5%) Most important aspect of plastic is waste management Jambeck et al., Science 2015, 347, 768-771
Important message The types of plastics we use will not change in a big way in the next century They are relatively Green in terms of the energy and material that goes into their production The way we treat them after use is poor many materials are poorly designed
85% of organic carbon is in the form of carbohydrates Carbohydrates Starch alone cannot form films with satisfactory mechanical properties Hygroscopic nature of starch dictates this material is unsuitable for high-moisture and liquid food products. Most biomaterials now produced are composites of starch and biopolymers.
Range of materials with different green credentials Biodegradable Plastics Cellulose based film Polyethylene starch composites PLA- starch composites PLA degrades in 100 days in industrial composter
Biodegradable Polymers PCL polycaprolactone Not-renewable (crude oil) PLA polylactic acid Biodegradable Renewable (Lactic acid formed by fermentation of corn starch) More expensive than petroleum based polymers
Starch Starches from a number of different sources Made up of amylose (linear) and amylopectin (branched) Ratios and molecular weight of respective components changes with starch type Typically 10-20% amylose and 80-90% amylopectin Different flour gives different bread!
Pumpernickel Recipe 1 cup water 0.25 cup molasses 2 tablespoons vegetable oil 0.5 cup whole wheat 0.5 cup rye flour 0.25 cup cornmeal 2.25 cups bread flour 1.5 teaspoon salt 2 teaspoons active dry yeast 1 tsp caraway seed (optional) Starch-based materials Brioche Recipe 2 tsp dried yeast 3 tbsp milk, hand-hot 200 g strong white flour large pinch of salt 1 tbsp caster sugar 50 g butter 2 eggs, beaten
Is starch packaging viable? It takes 8 tonnes of potatoes to produce 1 tonne of starch which can make approx 43,500 trays. The typical 20% UK potato crop wastage, 1.2 million tonnes, is equivalent to 6.5 billion trays. One of the major supermarket chains uses 2.5 billion trays p.a. It would require 1.5 to 2 million tonnes of potatoes to replace all EPS and PVC food packaging in GB with potato starch based products.
This makes a material with improved physical properties Heating in the presence of a modifier Two starch molecules Limited interaction occurs between each of the molecules Modifier enables stronger interactions between molecules Modifier
Starch + Glycerol Glycerol is a waste material from the soap and biodiesel industry and can be used to plasticise starch. Not very strong
Starch and Salts We use salts to open up the starch structure Above approx. 70 C solution starts to gel Starch granules burst and start gelation Forms strongly interacting macromolecular structure 1:1 ratio of starch: modifier is baked and forms a solid cheese Starch Starch + Salt Similar to salt dough 2 parts flour, 1 part water and 1 part salt
Starch interacts with salts Slime
Mix a simple salt with a complexing agent Biodegradable salt and complexing agent Keeping the salt liquid Choline chloride A vitamin in chicken feed Urea A common fertiliser e.g. urea, acetamide or glycerol
Mix two solids to make a liquid Keeping the salt liquid
Transparent starch-based plastics Compression moulding starch with salts leads to clear sheet Rapid setting time (<5 min for 1 mm thick sheet) Strength comparable to HDPE Corn starch 1 kbar 160 o C 1 min
Thermoplastic wood MDF uses urea - formaldehyde and phenol formaldehyde resins Formaldehyde is a carcinogen and means that the boards cannot easily biodegrade Salt modified starch can also be used as a binder
Thermoplastic wood Starch board mixes wood fibre with salt and starch Easier to process than MDF a) sawn, routed, screwed and drilled b) glued and laminated c) lacquered d) Vacuum formed
Process has been scaled up Thermoplastic wood 1 x 1 x 0.017 m starch boards have been made
Thermoplastic wood 20 boards were made and demonstration cabinets were produced
Thermoplastic wood Because it is a thermoplastic it can be recycled The product is called Starboard Starch-based thermoplastic wood after forming (left), after grinding (centre) and then after reforming (right). This shows that it can be effectively recycled.
Food vs. Plastic Lots of controversy when crops are used for applications other than food. A lot of material is waste in food production. Straw Sugar cane Orange Banana L to r: banana peel, potato, orange peel and corn starch
The ultimate waste These boards are made from the ultimate waste 680,000 tonnes of this waste is thrown away each year in the UK at a cost of 1.1bn.
Eggshell plastic Approached by a company that produces boiled egg Waste is c.a. 1 tonne per day
Eggshell plastic Eggshell is just calcium carbonate (chalk) which can be cleaned, ground and used as a filler in plastic Can be used up to 40 wt % as a filler Gives plastics a hard wearing surface Process plant opened in 2015.
Conclusions Plastics must not be thought of as disposable More materials must be designed for recycling Better education required on the properties of materials Biomaterials are part, but not all, of the answer Smarter packaging needs to be developed
Acknowledgements Tariq Abolibda Omaymah Alaysuy Dr William Wise Dr Andrew Ballantyne Dr Stefan Davis Sheridan & C o